Preparation of methyl 2,3-anhydro- and 2,3-o-sulfinylfuranosides from unprotected furanosides using the Mitsunobu reaction

Article abstract of DOI:10.1055/s-2001-10806

A new two step procedure for the synthesis of methyl 2,3-anhydro-α-D-lyxofuranoside and methyl 2,3-anhydro-β-D-ribofuranoside from D-xylose involving the intramolecular Mitsunobu reaction is presented. Likewise, methyl 2,3-anhydro-α-L-lyxofuranoside is obtained from L-arabinose. Cyclic sulfites with D-ribo configuration, synthetic equivalents of the corresponding anhydrosugars, are prepared in three steps from D-ribose.

Full text of DOI:10.1055/s-2001-10806

PAPER
229
Preparation of Methyl 2,3-Anhydro- and 2,3-O-Sulfinylfuranosides from
Unprotected Furanosides Using the Mitsunobu Reaction
Oliver Schulze,a Jürgen Voss,a* Gunadi Adiwidjajab
aInstitut für Organische Chemie der Universität Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
bMineralogisch-Petrographisches Institut der Universität Hamburg, Grindelallee 48, 20146 Hamburg, Germany
Fax +49(040)428385592; E-mail: voss@chemie.uni-hamburg.de
Received 14 April 2000; revised 13 October 2000
Several steps are however necessary to prepare these an-
hydrofuranosides. The synthesis of methyl 2,3-anhydro-
D-lyxofuranoside (4)3 and methyl 2,3-anhydro-D-ribo-
furanoside (1)1 from D-xylose (2) requires five or seven
Abstract: A new two step procedure for the synthesis of methyl
2,3-anhydro-a-D-lyxofuranoside and methyl 2,3-anhydro-b-D-ribo-
furanoside from D-xylose involving the intramolecular Mitsunobu
reaction is presented. Likewise, methyl 2,3-anhydro-a-L-lyxofura-
noside is obtained from L-arabinose. Cyclic sulfites with steps, respectively. 3,5-Anhydro-D-xylofuranoside (3)4 is
D-ribo configuration, synthetic equivalents of the corresponding an-
prepared from 1 in an eighth step (Scheme 2).
hydrosugars, are prepared in three steps from D-ribose.
Although the yields of the individual steps are generally
Key words: carbohydrates, epoxides, Mitsunobu reaction, sulfites,
high, a more facile synthesis is desirable. Since it has been
X-ray structure analysis
shown that 3,5-anhydro-1,2-O-isopropylidene-a-D-xylo-
furanose 6 can be prepared from 2 via 1,2-O-isopropyl-
idene-a-D-xylofuranose (5) by use of the Mitsunobu
reaction5 (Scheme 3), we have now investigated an analo-
gous sequence using unprotected methyl pentofurano-
sides and designed alternatives to the multistep
procedures for the preparation of 2,3-anhydro-pentofura-
nosides.
Strained carbohydrates, like 2,3- and 3,5-anhydrofurano-
sides, are important compounds since the oxirane- or ox-
etane substructure can be cleaved easily by various
nucleophiles to yield pentofuranosides, exhibiting a con-
figuration which depends on the anhydrosugar that was
used as starting material1 (cf. e. g., Scheme 1). The same
is true for the corresponding cyclic sulfites or sulfates,
which, due to their good leaving groups, also readily react
with nucleophiles.2 The regioselectivity of the nucleo-
philic attack depends on the kind of anomer, the nature of
the nucleophile and of the reaction conditions.
Methyl pentofuranosides were prepared according to the
procedure described by Anker et al. for xylose3 to give
anomeric mixtures in good yields. The anomers could be
separated by column chromatography. Only D-lyxose
gave low yields because the formation of pyranosides was
favoured.
Scheme 1
Scheme 2
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York

230
O. Schulze et al.
PAPER
Scheme 3
When the Mitsunobu reaction was performed using the The synthesized anhydrosugars are identical with those
methyl D-xylofuranosides 7 as starting compounds, the prepared in the conventional way.1,3 Since it was possible
expected oxetanes 3 were not obtained. Instead, the ox- to crystallize 4a and its a-L-enantiomer 9a, we could per-
iranes 1b and 4a were formed. Surprisingly, not even trac- form an X-ray diffraction study of both enantiomers that
es of the corresponding anomers 1a or 4b could be confirmed our results (Figure 1).
detected, indicating that 7a exclusively leads to the lyxo-
configurated product 4a, whereas the corresponding
b-anomer 7b exclusively leads to the ribo-configurated
product 1b (Scheme 3). If the anomeric mixture of methyl
D-xylofuranosides 7 is used as starting material the same
product mixture, 1b plus 4a, is formed according to the
NMR spectrum. The separation of the two products is,
however, difficult and separation of the anomers 7a and
7b before performing the Mitsunobu reaction is favour-
able.
Under the same conditions, methyl a-L-arabinofuranoside
(8a) yielded methyl 2,3-anhydro-a-L-lyxofuranoside
(9a), the enantiomer of 4a (Scheme 4), whereas 8b did not
react at all and was recovered nearly quantitatively. The
methyl ribofuranosides (10) led to complex product mix-
tures under the Mitsunobu conditions.
Figure 1 ORTEP view of the X-ray diffraction structure of 4a with
atom numbering. Thermal ellipsoids are drawn at the 50% probability
level.
In a more complicated way but also using the Mitsunobu
reaction Martin et al.,6 synthesized methyl 2,3-anhydro-a-
D-lyxofuranoside (4a) from methyl a-D-arabinofurano-
side. They proposed a 1,3,2-dioxa-l5-phosphorinane as
intermediate (Figure 2). An analogous intermediate could
explain the formation of 1b starting from 7b. Of course
these intermediates are reasonable but the inability of 8b
to react cannot be explained. Furthermore the formation
of 4a from 7a can hardly be explained because the corre-
sponding
1,3,2-dioxa-l5-phosphepane
intermediate
Scheme 4
seems to be unlikely in our opinion. Obviously the de-
tailed mechanism of the intramolecular Mitsunobu reac-
tion is not fully understood.
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Preparation of Methyl 2,3-Anhydro- and 2,3-O-Sulfinylfuranosides
231
Mps were determined by the use of an Electrothermal apparatus
(values are corrected). IR spectra were measured with an ATI Matt-
son Genesis spectrometer. NMR spectra were recorded with a Bruk-
er AMX 400 spectrometer. Chemical shifts (ppm) are related to
TMS (1H and 13C). Standard correlation techniques (H,H-COSY,
HMQC, HMBC, DEPT) were used for assignments. Mass spectra
were measured on Varian CH 7 (EI, 70 eV) and VG Analytical 70-
250 S (HRMS) apparatus. Optical rotations were measured on a
Perkin-Elmer Polarimeter 341. TLC was carried out on E. Merck
PF254 foils (detection: UV light, EtOH-H2SO4 spray / 200 °C), and
column chromatography on E. Merck Kieselgel 60 (70-230 mesh).
Solvents were purified and dried according to standard laboratory
procedures.9
Figure 2 A proposed 1,3,2-dioxa-l5-phosphorinane intermediate
[6].
As mentioned earlier, cyclic sulfites are useful synthetic
equivalents of anhydrosugars.2 These compounds can eas-
ily be obtained from ribofuranoside derivatives if their
primary hydroxy groups are protected.7 Since we were in-
terested in the synthesis of thioanhydrosugars, which can
be prepared by cleavage of thioacetates and subsequent
intramolecular nucleophilic attack on a leaving group,8 we
used the thio Mitsunobu reaction to introduce an acetyl-
thio group at the 5-position of 10b. This reaction was
highly chemoselective. No reaction at the secondary hy-
droxy groups was observed. The reaction of 11b with
thionyl chloride led to a diastereomeric mixture of two
sulfites 12b, which could not be separated chromato-
graphically. However the minor exo-diastereomer (exo-
12b) crystallized from methanol (Scheme 5). The struc-
ture of this isomer was confirmed by an X-ray diffraction
study (Figure 3).
X-ray Structure Analysis
The crystal data and a summary of experimental details for 4a, 9a
and exo-12b are given in Table 1. In all cases data collection was
performed on a KappaCCD Nonius diffractometer, with graphite
monochromated Mo Ka radiation (l = 0.71073 Å) in the rotation F
scan mode at a temperature of 293(2) K. Cell parameters were de-
termined by least-squares refinement of the angular settings of 1344
reflections with Q = 1.00°-27.48° (4a), 267 reflections with
Q = 1.00°-27.48° (9a) and of 646 reflections with Q = 11°-25°
(exo-12b). The structures were solved by direct methods using the
SIR-9710 program, and refined by full-matrix-block least-squares
on F2 using all data and the SHELXL-9711 program. Hydrogen po-
sitions were obtained by difference Fourier synthesis and / or geo-
metrical methods. Full crystallographic details, excluding structure
factors, have been deposited with the Cambridge Crystallographic
Data Centre. These data may be obtained, on request, from the
CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K.
Tel.+441223336408, Fax +441223336033, E-mail: depos-
it@ccdc.cam.ac.uk under the deposition numbers CCDC-142691
(4a), 142692 (9a) and 142690 (exo-12b).
Methyl Aldopentofuranosides; General Procedure
The aldopentose (5.00 g, 33.3 mmol) was added to a methanolic
HCl solution prepared from acetyl chloride (1 mL, 14.0 mmol) and
MeOH (100 mL). When all the starting material was consumed
(TLC detection), Ag2CO3 (3.0 g, 10.9 mmol) was added and the re-
action mixture was stirred over night. After filtration through Celite,
the solvent was evaporated and the resulting residue was purified by
column chromatography (silica gel, EtOAc/EtOH, 3:1) in order to
separate the anomers.
Mitsunobu Reaction of Methyl Aldopentofuranosides
Diisopropyl azodicarboxylate (1.2 mL, 5.97 mmol) was added to a
solution of triphenylphosphine (1.58 g, 6.03 mmol) in dry pyridine
(17 mL). After 10 min., a solution of methyl aldopentofuranoside
(0.50 g, 2.32 mmol) in pyridine (3 mL) was added. Then the reac-
tion mixture was stirred at 80 °C until the starting material was con-
sumed (TLC monitoring, 1 h for 7a/7b and 3 h for 8a). After
vacuum evaporation of the solvent, the residue was filtered through
Figure 3 ORTEP view of the X-ray diffraction structure of exo-12b
with atom numbering. Thermal ellipsoids are drawn at the 50% pro-
bability level.
Scheme 5
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York

232
O. Schulze et al.
PAPER
Table 1 Crystal Data and Structure Refinement for 4a, 9a and exo-12b
4a
9a
exo-12b
Molecular formular
Molecular weight (g Mol-1)
Crystal system
C6H10O4
146.14
monoclinic
P21
C6H10O4
146.14
monoclinic
P21
C8H12O6S2
268.30
monoclinic
P21
Space group
Unit cell dimensions
a = 8.908(1) Å
b = 4.444(1) Å
c = 9.138(1) Å
α = γ = 90°
a = 8.905(1) Å
b = 4.444(1) Å
c = 9.139(1) Å
α = γ = 90°
β = 100.80(1)°
355.26(1)
a = 11.308(1) Å
b = 4.588(1) Å
c = 12.433(1) Å
α = γ = 90°
β = 112.84(1)°
594.46(15)
2
0.35 × 0.28 × 0.22
1.78-25.00
-13£h£13; -5£k£5; -14£l£14
3275
β = 100.81(1)°
355.33(1)
Volume (ų)
Z (molecules per cell)
2
2
Crystal size (mm3)
0.47 × 0.21 × 0.11
2.27-27.29
0£h£11; -5£k£5; -11£l£11
7030
1595
1456
0.38 × 0.25 × 0.22
2.27-27.57
0£h£11; -5£k£5; -11£l£11
16507
1591
1438
q Range for data collection (°)
Index ranges
Reflections collected
Independent reflections
Reflections with I≥2s(I)
Refinement method
2090
2017
full-matrix-block least-squares
full-matrix-block least-squares
full-matrix-block least-squares
on F2
on F2
on F2
Function minimized
Sw(Fo -Fc2)2, w = 1/
Sw(Fo -Fc )2, w = 1/
Sw(Fo -Fc )2, w = 1/
2
2
2
2
2
[s2(Fo )+(0.0776P)2+0.0194P],
where P = (Fo +2Fc )/3
geom and difmap
[s2(Fo )+(0.1032P)2+0.0344P],
[s2(Fo )+(0.0816P)2+0.1233P],
2
2
2
2
2
2
2
where P = (Fo +2Fc2)/3
where P = (Fo +2Fc2)/3
H-atom refinement
geom and difmap
geom
Final R indices [I≥2s(I)]
R1 = 0.0341, wR2 = 0.1028
R1 = 0.0442, wR2 = 0.1235
R1 = 0.0381, wR2 = 0.0980
silica gel (EtOAc) and then purified by column chromatography
mL) and filtered. The filtrate was washed with light petroleum:Et2O
(1:1) (5 ¥ 50 mL each), then saturated with NaCl and extracted with
CHCl3 (5 ¥ 100 mL). After drying (MgSO4), filtration, and evapo-
ration, the residue was purified by column chromatography (silica
gel, EtOAc, Rf 0.65) to yield 11b (7.47 g, 33.6 mmol, 71%) as a pale
yellow syrup.
(silica gel, EtOAc). Compound 7a yielded 4a (0.19 g, 1.30 mmol,
20
56%) as colourless needles; mp: 83 °C (lit.1 mp: 78-80 °C); [a]D
20
84.9° (c 1.0, CHCl3) [lit.1 [a]D 65.7 (c 0.42, H2O)]; Rf 0.58
(EtOAc). Compound 7b yielded 1b (0.24 g, 1.64 mmol, 71%) as a
colourless syrup; bp: 72 °C (0.05 mm) [lit.12 bp: 48 °C (0.005 mm)];
[a]D20 -122.7° (c 1.0, CHCl3) [lit.12 [a]D28 -109° (c 1.98, H2O)];Rf
0.59 (EtOAc). Compound 8a yielded 9a (0.20 g, 1.37 mmol, 59%)
IR (film): n = 3407 (O-H), 2931, 2834 (C-H), 1692 (C=O), 1196,
1128, 1103, 1029 (C-O) cm-1.
20
as colourless needles; mp: 82 °C; [a]D -83.9° (c 1.0, CHCl3); Rf
1H NMR (400 MHz, D2O): d = 2.40 (s, 3H, SAc), 3.13 (dd, 1H, H-
5), 3.30 (dd, 1H, H-5'), 3.36 (s, 3H, OMe), 4.04 (d, 1H, H-2), 4.05-
4.15 (m, 2H, H-3, H-4), 4.73 (HDO), 4.85 (s, 1H, H-1). J1,2 = 0,
J2,3 = 4.2, J4,5 = 6.3, J4,5’ = 4.4, J5,5’ = 14.3 Hz.
0.57 (EtOAc). Compound 9b did not react even after prolonged stir-
ring under reflux. Compounds 10a and 10b yielded complex mix-
tures. The spectroscopical data of 4a and 1b were in accordance
with those reported in the literature.1,3,12
13C NMR (101 MHz, CDCl3): d = 30.36 (SAc), 32.40 (C-5), 55.54
(OMe), 73.69 (C-3), 74.78 (C-2), 81.07 (C-4), 108.32 (C-1), 200.62
(C=O).
Methyl 5-S-Acetyl-5-thio-b-D-ribofuranoside (11b)
A cooled (0 °C) solution of methyl b-D-ribofuranoside (7.75 g,
47.2 mmol) and freshly distilled thioacetic acid (4.3 mL, 60.4
mmol) in THF (290 mL) was added to a cooled (0 °C) mixture of
triphenylphosphine (14.79 g, 56.4 mmol) and diisopropyl azodicar-
boxylate (10.8 mL, 55.5 mmol) in THF (190 mL). The reaction mix-
ture was allowed to warm to r.t. and stirred over night. After
evaporation of the solvent, the residue was suspended in H2O (100
Methyl 5-S-Acetyl-2,3-O-sulfinyl-5-thio-b-D-ribofuranoside
(12b)
Et3N (10.2 mL, 73.6 mmol) and a solution of thionyl chloride
(2.7 mL, 37.2 mmol) in THF (7 mL) were added to a solution of me-
thyl 5-S-acetyl-5-thio-b-D-ribofuranoside (4.02 g, 18.1 mmol) in
THF (70 mL) at -20 °C. After 3 h, the reaction mixture was diluted
with EtOAc (100 mL) and washed several times with brine (70 mL
each). After drying (MgSO4), filtration, and evaporation of the sol-
vent, the residue was purified by column chromatography (470 g
silica gel, Et2O) yielding a diastereomeric mixture of the products
(4.22 g, 87%, Rf 0.92) as a yellow solid. According to the 1H NMR
spectrum, the ratio of the two diastereomers was 125:100 in favour
of endo-12b. The minor isomer exo-12b crystallized from MeOH as
colourless needles (mp: 113 °C). Its structure was verified by an X-
ray diffraction study.
Table 2 Yields and Rf Values of Methyl Aldopentofuranosides
a-anomer
Yield
b-anomer
Yield
Rf
Rf
(%)
(%)
D-xylose
D-ribose
L-arabinose
D-lyxose
45.6
20.0
21.8
3.2
0.53
0.47
0.56
0.59
54.3
70.9
62.6
0
0.58
0.63
0.43
–
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Preparation of Methyl 2,3-Anhydro- and 2,3-O-Sulfinylfuranosides
233
Table 3 1H NMR Data [400 MHz, D2O, d (ppm), J (Hz)] of Methyl Aldopentofuranosides
Furanoside
Nr.
1-H
2-H
3-H
4-H
5-H
5’-H
OMe
HDO
J1,2
J2,3
J3,4
J4,5
J4,5’ J5,5’
a-D-xylo
b-D-xylo
a-D-ribo
7a
7b
4.78
4.80
5.18
5.07
4.83
4.85
4.83
3.92
4.02
4.30
4.20
3.96
4.10
3.99
4.07
4.13
3.92
4.33
3.85
3.96
4.21
4.03
4.26
4.29
4.18
3.94
3.84
4.13
3.48
3.64
3.85
3.78
3.60
3.58
3.62
3.55
3.75
3.93
3.97
3.72
3.72
3.70
3.23
3.30
3.62
3.57
3.32
3.38
3.32
4.58
4.69
4.94
4.92
4.65
4.71
4.66
4.5
0
5.7
1.7
6.3
4.8
3.4
7.9
4.8
0
6.0
7.7
4.6
6.5
5.8
7.0
6.8
3.8
4.4
3.4
3.4
3.4
3.5
4.3
12.2
11.9
12.3
12.3
12.3
12.2
11.9
5.1
3.4
6.9
5.9
7.0
ca. 4.3
10a
10b
8a
4.4
0.9
1.5
4.6
3.7
b-D-ribo
a-L-arabino
b-L-arabino
a-D-lyxo
8b
Table 4 13C NMR Data [101 MHz, D2O, d (ppm)] of Methyl Aldopentofuranosides
Furanoside
Nr.
1-C
2-C
3-C
4-C
5-C
OMe
a-D-xylo
b-D-xylo
a-D-ribo
7a
7b
102.38
108.98
105.25
108.31
108.64
102.49
108.48
77.05
80.22
73.18
74.57
81.04a
76.65
76.33
75.29
75.29
71.77
71.16
76.68
74.82
71.37
78.61
82.91
86.58
83.20
84.22a
82.30
80.71
60.83
61.43
63.61
63.16
61.54
63.42
60.50
55.95
55.54
57.50
55.50
55.24
55.43
56.26
10a
10b
8a
b-D-ribo
a-L-arabino
b-L-arabino
a-D-lyxo
8b
a Assignment not unequivocal.
Table 5 1H NMR Data [400 MHz, CDCl3/TMS, d (ppm), J (Hz)] of Methyl 2,3-Anhydro-aldopentofuranosides
Furanoside
Nr.
1-H
2-H
3-H
4-H
5-H
5’-H
OMe
J1,2
J2,3
J3,4
J4,5
J4,5’
J5,5’
a-D-riboa
b-D-ribo
a-D-lyxo
a-L-lyxoc
b-D-lyxob
1a
1b
4a
9a
4b
5.21
4.97
4.97
4.97
5.01
3.80
3.78d
3.66
3.66
3.71
3.74
3.71d
3.76
3.76
3.73
4.32
4.27
4.13
4.13
4.03
3.67
3.67
3.86
3.85
3.86
3.71
3.72
3.86
3.85
3.90
3.51
3.47
3.43
3.43
3.53
0.7
0
0
0
0.6
2.9
2.7
2.9
2.9
3.0
0
0
0.6
0.5
0.9
3.6
3.4
5.3
5.3
5.5
3.6
3.4
5.3
5.3
5.6
11.5
12.3
–
–
11.3
a Only prepared according to lit.1
b Only prepared according to lit.3
c Only prepared by Mitsunobu reaction, this paper.
d Assignment not unequivocal.
Diastereomeric Mixture
EI MS: m/z (%) 208 (2, M+-O-CH-OCH3), 179 (9), 155 (2), 144
(2), 121 (4), 115 (2), 101 (9), 87 (6), 85 (9), 84 (7), 73 (8), 59 (7),
45 (31), 43 (100, CO-CH3).
Table 6 13C NMR Data [101 MHz, CDCl3/TMS, d (ppm)] of Me-
thyl 2,3-Anhydro-aldopentofuranosides
FAB MS (m-NBA): m/z (%) 269 (M++1).
Furanoside Nr. 1-C
2-C
3-C
4-C
5-C
OMe
Anal. Calcd for C8H12O6S2: C, 35.81; H, 4.51; S, 23.90. Found: C,
35.93; H, 4.42; S 23.98.
a-D-riboa 1a 102.76 56.35 57.57 78.82 62.90 57.57
b-D-ribo
1b 102.26 55.07d 56.21d 79.59 62.78 55.96
endo-12b:
a-D-lyxo 4a 102.23 55.86 54.10 76.36 61.65 55.61
a-L-lyxoc 9a 102.22 55.85 54.09 76.38 61.59 55.60
b-D-lyxob 4b 102.45 55.41 54.92 76.80 61.81 56.94
1H NMR (400 MHz, CDCl3): d = 2.39 (s, 3H, SAc), 3.08 (dd, 1H,
H-5), 3.24 (dd, 1H, H-5’), 3.43 (s, 3H, OMe), 4.57 (ddd, 1H, H-4),
5.11 (dd, 1H, H-3), 5.13 (d, 1H, H-2), 5.30 (s, 1H, H-1). J1,2 = 0,
J2,3 = 6.6, J3,4 = 0.9, J4,5 = 6.7, J4,5’ = 8.8, J5,5’ = 13.9 Hz.
a Only prepared according to lit.1
b Only prepared according to lit.3
13C NMR (101 MHz, CDCl3): d = 30.57 (SAc), 32.39 (C-5), 55.47
(OMe), 85.29 (C-4), 89.54, 91.02, 108.78 (C-1), 194.66 (C=O).
c Only prepared by Mitsunobu reaction, this paper.
d Assignment not unequivocal.
exo-12b:
[a]D20 -60.8° (c 1.0, CHCl3).
IR (KBr): n = 3005, 2993, 2957, 2943, 2914, 2839 (C-H), 1691
(C=O), 1207 (S=O), 1145, 1107, 1068, 1039 (C-O), 690 (S-O)
cm-1.
1H NMR (400 MHz, CDCl3): d = 2.39 (s, 3H, SAc), 3.11 (dd, 1H,
H-5), 3.22 (dd, 1H, H-5'), 3.41 (s, 3H, OMe), 4.31 (ddd, 1H, H-4),
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York

234
O. Schulze et al.
PAPER
5.08 (s, 1H, H-1), 5.33 (d, 1H, H-2 or H-3), 5.35 (d, 1H, H-2 or H-
3). J1,2 = 0, J2,3 = 6.2, J3,4 = 0.4, J4,5 = 6.8, J4,5’ = 9.0, J5,5’ = 13.9 Hz.
(6) Martin, M. G.; Ganem, B.; Rasmussen, J. R. Carbohydr. Res.
1983, 123, 332.
(7) Dauban, P.; Chiaroni, A.; Riche, C.; Dodd, R. H. J. Org.
Chem. 1996, 61, 2488.
(8) Voss, J.; Schulze, O.; Olbrich, F.; Adiwidjaja, G. Phosphorus,
Sulfur Silicon Relat. Elem. 1997, 120-121, 389.
(9) Autorenkollektiv, Organikum, 19th ed., Johann Ambrosius
Barth Verlag: Leipzig 1993, pp 659-681.
13C NMR (101 MHz, CDCl3): d = 30.57 (SAc), 32.05 (C-5), 55.40
(OMe), 84.58 (C-4), 86.69 (C-3), 87.85 (C-2), 108.34 (C-1), 194.45
(C=O).
HR FAB MS (m-NBA) [M++H]: calcd 269.0154. Found: 269.0102
(M++1).
(10) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.;
Moliterni, A. G. G.; Burla, M. C.; Polidori, G.; Camalli, M.;
Spagna, R. SIR97: A Package for Crystal Structure Solution
by Direct Methods and Refinement; Bari, Perugia, Rome,
Italy, 1997.
(11) Sheldrick, G. M. SHELXL-97: Program for Crystal Structure
Refinement; University of Göttingen, Göttingen, Germany,
1997.
Anal. Calcd for C8H12O6S2: C, 35.81; H, 4.51; S, 23.90. Found: C,
35.84; H, 4.44; S 24.10.
References
(1) Unger, F. M.; Christian, R.; Waldstätten, P. Carbohydr. Res.
1978, 67, 257; and references cited therein.
(2) Lohray, B. B. Synthesis 1992, 1035.
(3) Thomé, M. A.; Giudicelli, M. B.; Picq, D.; Anker, D. J.
Carbohydr. Chem. 1991, 10, 923.
(12) Anderson, C. D.; Goodman, L.; Baker, B. R. J. Am. Chem.
Soc. 1958, 80, 5247.
(4) Buchanan, J. G. Methods Carbohydr. Chem. 1972, 6, 135.
(5) Moravcová, J.; Rollin, P.; Lorin, C.; Gardon, V.; »apková, J.;
MazáË, J. J. Carbohydr. Chem. 1997, 16, 113; and references
cited therein.
Article Identifier:
1437-210X,E;2001,0,02,0229,0234,ftx,en;H02300SS.pdf
Synthesis 2001, No. 2, 229–234 ISSN 0039-7881 © Thieme Stuttgart · New York